Chlorination of hydrocarbons



A TTO'R/VEY Iii/225W aemmfmmn? 62A Tammy/w 11v VENTORS c F TEICHMANN EI'AL CHLORINATION OF HYDROCARBONS Filed Apr-il 1, 1933 Sept. 17, 1935.

Patented Sept. 17, 1935 UNITED STATES 2,015,044 CHLORINATION or nrnnocaanous Charles F. 'Tcichmann, Hugo Klein, and Carl 1. Bathemacher, New York, N. Y.

Application April 1, 1933, Serial No. 663,936

4 Claim.

This invention relates to the halogenation of hydrocarbons and more particularly to a process of chlorinating hydrocarbons whereby monochlor compounds of the hydrocarbons are selec- 5 tively produced. 4

The invention contemplates a method of chlorinating hydrocarbons wherein unreacted hydrocarbons are initially reacted with a reagent consisting of poly-chlor derivatives oi the hydrocarbon in the presence of ultra-violet light to form mono-chlor derivatives of the hydrocarbon. The products of this reaction are then treated with tree chlorine to bring about the chlorination of any remainingunreacted hydrocarbons. As products of the chlorination reaction, there are formed not only mcno-chlor but also poly-chlor derivatives as well as hydrogen chloride. The chlor derivatives, after freeing them from hydrogen chloride, are separated'into two fractions, one consisting of the mono-chlor compounds, and the other, of poly-chlor compounds. The former are collected 'as a final product while the latter are returned and reacted with fresh unreacted hydrocarbons in the manner previously described.

Chlorination reactions may be carried out either in the vapor phase or in the liquid phase. In the latter, the rate of chlorination is usually quite low and, as a result, recourse has been had to the use of catalysts for accelerating the reaction. Amcng the catalysts generally-used are included finely-divided adsorbents. metallic chlorides, iodine and ultra-violet light. It is observed that both with and without the catalysts, poly-chlor compounds in considerable quantity are produced in addition to the desired monochlor compounds.

By carrying out the chlorination reaction in the vapor phase, much more rapid reaction is 40 possible. However, the inherent disadvantage observed in the liquid phase operation is also observed here, namely, that, in addition to the formation of the desirable mono-chlor compounds, considerable proportions of the dland tIi-ChlOr derivatives are formed. It is also well known that the vapor phase reaction suffers from the further disadvantage that the reaction is highlyexothermic and extreme care and control thereof is necessary. 50 The inventors have discovered that, when the undesirable poly-chlor compounds, which are 5 posed in the form of a spray or fog to the action side of the pump I2.

of ultra-violet light, the formation of considerable quantities of the desired mono-chlor compounds may be brought about. Although no theoretical explanation of the reaction is advanced. it is believed that, under the influence of 6 the ultra-violet light radiation, a molecular rearrangement tak'es place, the chlorine molecules of the poly-chlor derivatives becoming labile or active and displacing a hydrogen molecule of I the unreacted hydrocarbon, the hydrogen so dls- 10 placed assuming the position of the chlorine in what was formerly the poly-chlor compounds. That this reaction takes place, in some such manner, is evidenced by the fact that very little liberation. of hydrochloric acid is observed in the 15 reaction.

We have also found that, when the reaction products produced as a result of the above reaction are subjected to reaction with chlorine to bring about the chlorination/ of the remaining 20 quantities of unchlorinated/ hydrocarbons, no further radiation with ultra violet light is neo essary, the initial radiation su'flicing for the catch ysis of the reaction.

It is also noted that the reaction with chlorine 25 is quite rapid and smooth! which may be'due to the fact that the solubility of the chlorine in the unchlorinated hydrocarbons is increased by the presence of mono-chlor compounds in which both the chlorine and the unchlorinated hydro- 30 carbons are mutually miscible.

In reacting the unchlorinated hydrocarbons with the poly-chlor derivatives, the reaction may be carried out either in the liquid phase or in the vapor phase. However, the most eificient method appears to consist. in atcrnizing both of the reactants to form a mist or fog and then radiating the same with ultra-violet light. In this way, even and, rapid interaction may be brought about. As regards the subsequent chlorination of the products of this reaction, this, too, is most satisfactorily effected by atomizing the mixture of hydrocarbons and chlor derivatives and acting upon the resultant fog with chlorine.

The above described invention has been incorporated in a chlorination procedure which will be readily understood by reference to the accompanying drawing which shows in diagrammatic sectional elevation a desirable apparatus for carrying out the process.

The numeral l0 indicates astorage for hydrocarbons to be chlorinated. This storage vessel is connected by means of the line I l with the intake This pump discharges regulation 01' the temperature within the cham- A lower point of the reaction chamber is iltted with a drawoii line 23 controlled by the her.

valve 24, which line discharges through the spray nozzle 25 into the reaction chamber II. Into the line 2! at a point intermediate the reaction chamberj'l'l and the control valve 23 there is fitted a line "controlled by the valve Ii.

ilhe reaction chamber 26 may be of a construction similar to that of chamber I except icr the fact that it need not be provided with windows of ultra-violet pervious material. It is provided with temperature control means in the icrm oi a heating or cooling coil 21 and with a drawoiiline- 2! controlled by the expansion valve 2| .whichline-connects the bottom of the reaction chamber with a lower point in the fractionatingtowerlL.

l The iractionating tower 3| may beoi any conventional construction suitable for the distillation and rectification of compounds having diflei'e' entboiling points. The i'i-actionating toweris fitted at its uppermost point with a vapor line 32 controllod by the valve 38 which leads to a hydro.-

chloric acid system, not shown; It is'provided at an upper point with a reflux N through which a coolant or refrigerant may be circulated-and at a lower point with swarming or heating coil 3|. An upper point in the iractionat ins tower is also preferably fitted with 'a' liquid drawoi! line "controlled by the valve 88 leading to the storagetank II. The bottom 01' the tower is provided with a drawoi! line controlled by the host controlled-valve ll which line connects with thelntake side of the pump 42. This pump,

in turn discharges through the line 3 controlled by the valve 44 into the mixing chamber I. The mixing chamber may be of any type suitable for the etlicient agitation of liquids and is preterably fitted with a mechanical mixing or agitating device. To the mixing chamber there is connected the storage tank 4! through the line II, the valve l1 and the pump ll. Themixingchainberls also fitted with a drawoii line ll controlled by the valve ii which leads to a separatorychamber II. The bottom of the separatory chamber isfitted with a liquid drawoii line is controlled by thef fioat controlled valve II while the top of the separator is fitted witha drawoii' line II which connects through the pump '1 and the valve I! with the coil 6| situated within the heating chamber ll through which a heating medium such as hot oil may be circulated. The outlet side of the coil I is connected through the line 02 cmtrolled by the valve II with the tractionating tower II at a lower point in its structure.

The tower as is fitted at its uppermost point with a vapor drawofi line it which leads to a-condensing system, not shown. The tower is also provided at an upper point with a refiux cool!! I coil l1 and at a lower point with a heating coil BI for imparting heat to the bottoms.wlthin the tower. The tractionating tower is provided at intermediate points in its structure with liquid aoiaou cmw'os j 'll' and' -licontrolled or the valves it II, which lines are manlioldedf to thejline ll, controlledby'the valve "ll,whi ch f line connectswith the intake side of the pumpin turn discharges throughlthe-, g

line 'llc'ontrolled by the valve 'll-intothe I! at a point. intermediate the valve IQ- and" the reaction chamber I.

The bottoms which remain as a the line 8. controlled by the valve it and passed to suitable storage, not, shown. 7

In the typical operation 0! the a petroleum hydrocarbon oil or a petroleum by; I drocarbon such, for example, as a pentane inc-'15 tion is drawn from the storage tank I. by means of the pump it and delivered under a pressure which may be as high as several hundred pounds per square inch to the line I! where it is mixed with poly-ch: compounds obtained from a. later 99 stage in the process, preferably in the of four parts oi pentane to each part at poly-.chlor compounds. The mixture oi the unchlorinated hydrocarbon and the poly-chior compounds is discharged in the term at a spray into the reaction as chamber I! wherein it is subjected in a finelydivided form to the rays of ultra violet light. The source of the ultra-violet light .is preferablysituated without the reaction chamber in orderi to prevent as far as possible the introduction of ,5 heat into the reaction. I

The temperature within the rtion chamber it must be kept within closely controlled limits in order to efiect the highest pos-' sibleconversion oi the poly-chlor compounds into "a mono-chlor compoimds. No specific temperatures can be given since the same is dependent upon the pressures used in the chlorination procsee. It is suillcient to say that the pressures ,used 7 must behigh enough to maintain the hy drocarbon, in thb case pentan substantially in the liquid phase. i

The products or the reaction which collect as a liquid at the bottom of the reactionfchamber- II are continuously withdrawn iromthat chameher into the line II into which a controlled quanf tity oi chlorine is simultaneously introduced through the line II controlled by the valve Ii. This mixture is then sprayed into the reaction chamber a whereinran extensive chlorination or I any remaining unchlorinated hydrocarbonstakes 7 place. The reaction mixture is not subjected to the action ot'ultra-violet light since ithas been. found that by irradiating the reaction mixture in the first reaction chamber, the molecules 01 the reactants are'made. sufiiciently active.

The quantity oi chlorine supplied through the line II is carefully controlled tolprevent as far as possible an unduly large formation of polychlor compounds. It-must berecognised that the chorination with chcrine as a reagentcannotbe to the iormationo! the mono-chlor com-- pounds alone since, in accordance with the recognized equilibria defined by chemical laws, certain definite percentagesot both the diand tri-chlor a corapounds' are necessarily formed as by-prodno The pressure maintained within the reaction chamber 86 is preferably somewhat lower than that existing within the reaction chamber It. The corresponding temperature in the reaction chamber 2' may be maintained within a somewhat higher range but must be closely controlled by the circulation of coolant through thecoil 21 to prevent any undesirable and unduly rapid re- 7Q;

residue at l; bottom of the tower 6| may be withdrawn through-1 action. The reaction mixture which collects at the bottom of the reaction 2. consists of a large percentage joi n onomhlor compounds together with small-l percentages oi poly-chlor com-'- pounds, unchlorinated hydrocarbons as well-as some dissolved hydrochloric acid 7 and excess. chlorine. This mixture is drawn oi! through the line 28 and through the control valve it and flashed into the iractionating tower ll wherein the chlorinated hydrocarbons are separated from. the hydrochloric acid, free chlorine and imchlorinated hydrocarbons. 4

. The temperature conditions within the iractionating tower are maintained within such limits as to permit of withdrawal of the hydrochloric acid gas and chlorine from the top of the tower through the vapor drawoi! line 32. These vapors may then be delivered to a hydrochloric acid recovery apparatus where the hydrochloric acid is freed from chlorine and concentrated. The'unchlorinated hydrocarbons which are separated in the course oi! the iractionation within the tower ii are drawnoii' through the line 81 controlled by the valve 38 and returned to the storage It for; unreacted hydrocarbons.

The moncand poly-chlor compounds collect at the bottom of the iractionating tower 'II in a pool of controlled'depth. These compounds are drawn oil in a controlled stream through the line 4| controlled by the automatic valve ti and led to the intake side of the pump 42 which delivers them under a pressure through the line 43 and the valve 44 into the agitating or mixing device 4! into which there is simultaneously pumped a controlled amount of wash water or preierably an aqueous alkaline solution'trom the tank ll. The agitation with the wash medium serves to remove from the chlor compounds any traces or either hydrochloric acid or tree chlorine that'are present therein.

The mixture of chlor compounds and wash medium is discharged from the mixing chamber ll through the line II and delivered into the settling and separatory chamber 52 wherein the chlor compounds are settled-free from the wash medium. The latter is continuously drawn oil in a controlled stream through the line II controlled by the valve 58 while the supernatant layer of chlor compounds is removed through the line I by the pump 51 and delivered thereby under an elevated pressure into the heating coil CI of the heater Ii. 1

In order to heat the contents of the coil I, 'there'is circulated through the space surrounding the coils a heating medium which may be oil or some similar non-volatile material. After the chlor compounds have been heated to a temperature suiiiciently high to permit of the vaporization of the monoand poly-chlor compounds, the heated compounds are delivered through the line 62 and the valve 03 and flashed into the tractionating tower t! which may be maintained at a pressure only slightly greater than atmospheric.

Under the conditions oi temperature and pressure obtaining within the iractionating tower, the monoand poly-chlor compounds of the hydrocarbon are substantially vaporized and, by properly controlling the temperature diflerence within the tower, the mono-chlor compounds may be taken 0! from the top of the tower through the line 66 as a definite fraction. The diand tri-chlor compounds, on the other hand, are taken oil as side fractions from the tower through the lines 10 and I! which leave the tower at intermediate points in its structure. The residues which collect at the bottom of the tower'consist oi-polymers as well as highly complex chlor de-, 'rivatives and these are drawn oil through the line I! controlled by the vaiveii and leadto a suitable storage. a

The diand tri-chlor compounds which are 1 produced as side fractions are-drawn oil through the line ll controlled by the valve It and (le v .livered to the pump 11 which,-in turn, delivers them under a suitable pressure into the line l! I! where they are mixed with unchlorinated hydrocarbons; v

Although the chlorination ct pentane has been described in the aioregoing example, the process isnotlimitedtoeitherdennitehydrocarbonsorll to definite fractions 0! hydrocarbons. It is a plicable to hydrocarbon mixtures consisting of widely varying constituents. Chlorination of di!-' terent compounds" requiru the application of diii'erent conditions so that no definite temperature or pressure ranges may be consistently given. It may be pointed out, however, that most elective reactions are obtainedwhm the pressures used are sumciently high to prevent any undue vaporization 01' either the hydrocarbon: or 5.

the poly-chlor derivatives thcreoi. Obviously many modifications and variations oi the invention, as hereinbei'ore set forth, may

-be made without departing from the spirit and scope thereof, and therefore only such limitations the hydrocarbons in-the presence ofultravioiet light and substantially in the liquid phase, then submitting the reaction products to a reactin with chlorine under such pressure as to maintain the reaction products substantially in the liquid phase whereby mono-chlor and poly-chlor compounds as well as hydrochloric acid' are formed, removing the hydrochloric acid and separatlng the chlor compounds into two fractions, the one comprising the mono-chlor derivatives and the other, the poly-chlor derivatives.

2. The process oi preparing mono-chlor derivatives oi' paraillnichydrocarbons which com- 50 prises initially reacting the hydrocarbons with a reagent consisting o1 poly-chlor derivatives of the hydrocarbons in the presence of ultra-violet light and substantially in the liquid phase, then submitting the reaction products to a reaction with chlorine under such pressure as to maintain the reaction products substantially in the liquid phase whereby mono-chlor and poly-chlor compounds as well as hydrochloric acid are formed, removing the hydrochloric acid, separating the chlor compounds into two fractions, the one comprising the mono-chlor derivatives and the other, the poly-chlor derivatives and recycling the latter to react with the unchlorinated hydrocarbon.

3. The process oi preparing mono-chlor de rivatives oi paraillnic hydrocarbons which comprises mixing the hydrocarbons with a reagent consisting of poly-chlor derivatives of the hydrocarbons to form a mixture, atomizing the mixture to form amist and subjecting the mist to reaction while maintained substantially in the liquid phase and in the presence 0! ultra-violet light, then mixing the reaction products with chlorine, atomizing the mixture to iorm a mist 75 while maintained substantially in the liquid phase whereby mono-chlor and poly-chlor compounds as well as hydrochloric acid are formed, removing the hydrochloric acid and separating the monochlor compounds from the poly-chlor compounds by distillation.

4. The process of preparing mono-chlor derivatives of paraflinic hydrocarbons which comprises mixing the hydrocarbons with a reagent consisting oi poly-chlor derivatives of the hydro carbons to form a mixture, atomizing the'mixture to form a mist and subjecting the mist to reaction in the presence of ultra-violet light ---bydistillation and recycling the latter to react with the unchlorinated hydrocarbon.

- CHARLES F. 'I'EICHMANN,

CARL P. RATHEMACHER. 

